KR20050067155A - Oxidizing heat treatment passivation of sulphide hydrotreatment catalyst - Google Patents
Oxidizing heat treatment passivation of sulphide hydrotreatment catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002161 passivation Methods 0.000 title claims abstract description 29
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title abstract description 19
- 238000010438 heat treatment Methods 0.000 title abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 41
- 229910052760 oxygen Inorganic materials 0.000 claims description 41
- 239000001301 oxygen Substances 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000011066 ex-situ storage Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 50
- 229910052757 nitrogen Inorganic materials 0.000 description 25
- 239000012298 atmosphere Substances 0.000 description 18
- 230000009257 reactivity Effects 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 238000005486 sulfidation Methods 0.000 description 14
- 238000005987 sulfurization reaction Methods 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000003622 immobilized catalyst Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007324 demetalation reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
- B01J37/14—Oxidising with gases containing free oxygen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
수소화처리 촉매는 일반적으로 탄화수소의 수소화 전환 반응, 특히 불포화 탄화수소의 수소화처리 반응 (예를 들면 수소화탈황화 반응, 수소화탈질소화 반응, 탈금속화 반응) 및 수소화 반응의 조합을 촉매 성능에 부여하기 위하여 사전에 황화 처리하여야만 하는 CoMo/Al203, NiMo/Al203 또는 NiW/Al203로 표시한 고형물과 같은 1 이상의 원소 주기율표의 VIII족 및 VI족의 원소 또는 이들 족으로부터의 다수의 원소의 조합이 결합된 무정형 또는 결정형 산화물 지지체 (예컨대 알루미나, 실리카, 실리카 알루미나, 제올라이트)를 포함한다. 이러한 촉매 작용 이전의 황화 단계는 2 가지의 상이한 방식으로 수행될 수 있다.Hydrotreating catalysts are generally used to impart a combination of hydroconversion reactions of hydrocarbons, in particular hydrotreating reactions of unsaturated hydrocarbons (e.g. hydrodesulfurization reactions, hydrodenitrification reactions, demetallation reactions) and hydrogenation reactions to the catalytic performance. Many of the elements of Groups VIII and VI of the Periodic Table of the Periodic Table, such as CoMo / Al 2 0 3 , NiMo / Al 2 0 3 or NiW / Al 2 0 3 , which must be sulfided in advance or from these groups Amorphous or crystalline oxide supports (such as alumina, silica, silica alumina, zeolites) to which a combination of elements of is bonded. The sulfidation step prior to this catalysis can be carried out in two different ways.
현장내에서의 황화 반응으로 지칭되는 제1의 반응은 산화물 형태의 촉매를 우선, 황화시키기 위한 탄화수소의 전환 반응기에 투입하는 것을 특징으로 한다. 본 출원인의 특허 (US-4,719,195, US-5,397,756, EP-A 785,022)에 기재된 바와 같은 현장외 예비황화로 지칭되는 제2의 반응은 촉매의 황화 또는 예비황화 반응을 탄화수소의 전환 반응기의 떨어져 있는 특정의 유닛, 특히 촉매의 사용 지점에서 이격된 국소 유닛에서 수행한다.The first reaction, called in-situ sulfidation, is characterized in that the catalyst in oxide form is first introduced into a hydrocarbon conversion reactor for sulfiding. A second reaction, referred to as off-site presulfurization, as described in the Applicant's patents (US-4,719,195, US-5,397,756, EP-A 785,022), allows the sulfiding or presulfurization of the catalyst to be carried out at the specific distance of the conversion reactor of the hydrocarbon. In the unit, especially in a local unit spaced apart from the point of use of the catalyst.
이와 같은 현장외 황화 방법의 구역내에서, 형성된 황화물상은 이의 반응도를 제한하고자 하는 보충 처리 없이도 차후의 조작을 방해하게 되는 주위 대기에 대한 반응도가 매우 높게 나타난다. 산화 대기와의 반응성은 유엔 표준으로 정의되는 2 가지 유형의 양상, 즉 발화성으로 알려진 양상 및 자동 발화로 알려진 양상으로 설명된다.Within the zone of this off-site sulfiding method, the formed sulfide phases exhibit very high reactivity to the surrounding atmosphere which would interfere with subsequent manipulation without the need for replenishment to limit their reactivity. Reactivity with an oxidizing atmosphere is explained by two types of aspects defined by the United Nations standards: those known as flammable and those known as autoignition.
화합물의 발화성은 산화 대기하에서 설정되는 자발 연소를 특징으로 한다. 자동 발화성은 140℃에서 특정의 조건하에서 생성물이 가열되는 경우, 신속한 산화 반응으로 인하여 상당한 온도로 승온되는 것을 특징으로 한다.The flammability of the compound is characterized by spontaneous combustion which is established under an oxidizing atmosphere. Auto-ignition is characterized in that when the product is heated at 140 ° C. under certain conditions, it is raised to a significant temperature due to the rapid oxidation reaction.
예비황화 방법으로부터 얻은 황화물상은 자가 가열을 나타내며, 이러한 단점을 치유하고 이러한 상을 부동화 상으로 하기 위하여, 종래 기술에서는 황화물상에서 소정량의 산소를 흡착시키도록 하는 것으로 이루어진다. 이러한 방법은 특정의 효과는 지니나, 종종 불충분하다. EP 0,707,890에는 30 ㎪ 미만 (바람직하게는 10%, 5% 또는 1% 미만)의 산소 분압하에서 산소 30 부피% 미만을 포함하는 가스류하에서 사전에 황화 처리하며, 이러한 처리는 상온에서 수행하는 것인 촉매의 산화 부동화 단계가 기재되어 있다. 또한, WO98/37,963에는 50℃ 이상의 온도에서 0.25∼21 ㎪의 산소 분압하의 0.25∼21 부피% (바람직하게는 0.5∼1.5 부피%)의 산소를 포함하는 가스류하에서 예비 황화 처리한 전환 반응 촉매의 산화 부동화 방법이 기재되어 있다. 미국 특허 제2002 000 394호 또는 문헌 [Louwers et al., vol. 144 No. 2, 1993-12, pages 579-596"]에는 정유 또는 석유화학에서의 산업적 규모로 사용되도록 하는 작업 조건에 결부되지 않고도, 촉매를 부동화시키는 방법이 기재되어 있다. 상기와 같이 기재된 처리가 황화 및 부동화된 촉매의 소량을 공기하에서 조작하기에 충분할 경우, 촉매의 수소화처리 유닛의 반응기의 대기하에서의 충전에 상당한 주의를 기울여야만 하는데, 이는 자동 발화 양상이 너무 지나치기 때문이다. 그래서, 가능한한 우수한 촉매 성능을 보유하면서도 자동 발화 온도를 승온시키는 방법에 대하여 연구하였다.The sulfide phase obtained from the presulfurization process exhibits self heating, and in order to cure this disadvantage and make this phase passivated, the prior art consists of adsorbing a predetermined amount of oxygen in the sulfide phase. This method has certain effects, but is often insufficient. EP 0,707,890 discloses a prior sulfidation under a gas stream comprising less than 30% by volume of oxygen at an oxygen partial pressure of less than 30 kPa (preferably less than 10%, 5% or 1%), which treatment is carried out at room temperature. The oxidation passivation step of the catalyst is described. WO 98 / 37,963 also discloses a conversion reaction catalyst subjected to presulfurization under a gas stream containing 0.25 to 21% by volume (preferably 0.5 to 1.5% by volume) of oxygen at a temperature of 50 ° C. or higher under a partial pressure of 0.25 to 21 kPa. Oxidative passivation methods are described. U.S. Patent No. 2002 000 394 or by Louwers et al., Vol. 144 No. 2, 1993-12, pages 579-596 ", describe a method for immobilizing a catalyst without being bound to operating conditions intended to be used on an industrial scale in oil refining or petrochemicals. If a small amount of immobilized catalyst is sufficient to operate under air, great care must be taken in the charging of the catalyst under the atmosphere of the reactor of the hydrotreatment unit, since the autoignition pattern is too high, so a good catalyst as possible The method of raising the autoignition temperature while maintaining the performance was studied.
그래서, 본 발명은 수증기의 존재 또는 부재하에서 산소 분압을 포함하는 가스류하에서의 열 처리에 의하여 촉매에 비-자동 발화 양상을 부여하게 되는 부동화 방법을 제안하고자 한다.Thus, the present invention seeks to propose a passivation method which imparts a non-automatic ignition pattern to the catalyst by heat treatment under a gas stream comprising oxygen partial pressure in the presence or absence of water vapor.
본 발명의 방법의 잇점은 하기와 같다. 종래의 기술의 방법을 사용하면, 물론 특정의 경우에서 대기중에서 황화물상을 처리할 수 있으나, 반면에 대기의 존재하에서 반응기내의 촉매의 충전은 이의 상당한 중량으로 인하여 촉매의 가열을 야기하며, 그리하여 위험한 환경을 유발하게 된다. 그래서, (특정의 사용자들은 이의 실시를 고집하기도 하나) 반응기내에서 대기하에서 촉매의 충전을 처리하는 것을 권하지 않게 되지만, 질소 대기하에서 더욱 안전하게 작업할 것을 권장하고 있다. 본 발명에 의한 방법을 사용하여, 황화물상 형태의 촉매에 의한 반응기의 대기하에서의 충전은 아무런 위험 없이 실시 가능하게 된다.The advantages of the process of the invention are as follows. Using the prior art methods, of course, in certain cases it is possible to treat the sulfide phase in the atmosphere, whereas the filling of the catalyst in the reactor in the presence of the atmosphere causes the heating of the catalyst due to its considerable weight and thus is dangerous It causes the environment. Thus, although certain users insist on doing this, it is not recommended to handle the filling of the catalyst under the atmosphere in the reactor, but it is recommended to work more safely under a nitrogen atmosphere. Using the process according to the invention, filling under the atmosphere of the reactor with catalysts in the sulfide phase form can be carried out without any risk.
보다 상세하게는, 본 발명은 산소 (예를 들면 건조 대기 또는 습윤 대기로부터 유래한 산소)를 포함하는 가스 (또는 가스류)의 존재하에서 열 처리에 의하여 촉매의 현장외 황화 반응 이후에 부동화 방법을 실시하는 것에 관한 것이다. 이러한 부동화 방법은 고정상으로 배치된 촉매 충전물에서 (예를 들면 튜브형 반응기내에서) 또는, 이동상, 특히 회전로, 유동상로, 대상로 또는 붕괴(croulant)로와 같은 이동상에 배치된 촉매 충전물에서 용이하게 수행될 수 있다. 본 발명에서, 황화물상은 고온, 즉 50℃ 초과, 또는 55℃ 이상, 바람직하게는 120℃ 이하, 또는 75℃∼120℃의 온도에서, 2 ㎪ 이상, 바람직하게는 7 ㎪ 이상의 산소 분압하의 가스에 의하여 처리한다. 분압은 21.3 ㎪ 이하가 일반적이다. 이는 덜한 가열상의 존재하에서 실시할 수 있다.More specifically, the present invention provides a process for passivation after off-site sulfidation of the catalyst by heat treatment in the presence of a gas (or gas stream) comprising oxygen (eg, oxygen derived from a dry atmosphere or a wet atmosphere). It is about performing. This passivation method is easy in a catalyst charge placed in a fixed bed (for example in a tubular reactor) or in a catalyst charge placed in a mobile phase such as a rotary furnace, a fluidized bed, a subject or a croulant furnace. Can be performed. In the present invention, the sulfide phase is subjected to a gas under an oxygen partial pressure of at least 2 Pa, preferably at least 7 Pa, at a high temperature, that is, above 50 ° C, or at a temperature of 55 ° C or higher, preferably 120 ° C or lower, or 75 ° C to 120 ° C. To deal with. The partial pressure is generally less than 21.3 kPa. This can be done in the presence of a less heated phase.
실시예에서 예시하는 바와 같이, 이러한 방법은 2 가지의 단계로 실시할 수 있는 것이 이로운데, 제1의 단계는 2 ㎪ 이상, 바람직하게는 7 ㎪ 이상의 산소 분압하에서 실시하고, 제2의 단계는 제1의 단계보다 높은 산소 분압하에서 실시하며, 제2의 단계는 발열이 소실되면 개시한다.As illustrated in the examples, it is advantageous that this method can be carried out in two stages, the first stage being carried out under an oxygen partial pressure of at least 2 Pa, preferably at least 7 Pa, and the second step being It is carried out under an oxygen partial pressure higher than the first stage, and the second stage starts when the heat generation is lost.
대기하에서 의도하는 처리를 실시하기 위하여, 특히 수소화처리 유닛에서의 충전시 예비황화 처리한 촉매의 자동 발화 양상을 감소시키도록 하는 본 발명의 바람직한 구체예에서, 21.3 ㎪를 달성할 수 있는 산소 분압 및, 2 ㎪ 이상의 바람직한 수소 분압하에서 그리고 수 포화 대기가 될 때까지의 산소 분압을 포함하는 습윤 가스류하의 온도에서 촉매를 처리한다.In order to carry out the intended treatment in the atmosphere, in particular in the preferred embodiment of the present invention to reduce the autoignition behavior of the presulfurized catalyst during charging in the hydrotreatment unit, an oxygen partial pressure capable of achieving 21.3 kPa and The catalyst is treated under a desired hydrogen partial pressure of at least 2 Pa and at a temperature under a wet gas stream comprising an oxygen partial pressure up to a water saturated atmosphere.
실시예 1: 촉매 제조의 기준예: 부동화 처리하지 않은 현장외 황화 반응Example 1: Reference Example of Catalyst Preparation Off-Site Sulfurization Reaction without Passivation
비표면적이 큰 (220 ㎡/g) 알루미나 지지체상에 결합된 산화물리브덴 18.9 중량% 및 산화코발트 4.2 중량%를 포함하는 수소화처리 촉매를 황화수소(H2S) 60 부피% 및 수소(H2) 40 부피%의 조성을 갖는 혼합물에 의하여 대기압하에서 황화 처리하였다. 촉매의 황화 반응은 2 가지의 단계로 얻는데, 제1의 단계는 조절된 온도 (5℃/분)로 승온된 단계에서 수행되며, 제2의 단계는 300℃의 황화 반응의 최종 온도에서 1.5 시간의 단계에서 수행한다. 황화 반응후, 촉매를 상온이 될 때가지 질소류하에서 냉각시킨다. 생성물의 일부를 황화 반응도 분석을 위하여 질소 대기하에 옮겨둔다. 나머지는 질소로부터 분리하고, 자동 발화 양상의 특성화 및 가스유의 수소화탈황 활성의 측정에 사용한다.A hydrotreating catalyst comprising 18.9% by weight of oxide ribidene and 4.2% by weight of cobalt oxide bonded on a large (220 m 2 / g) alumina support was subjected to 60% by volume of hydrogen sulfide (H 2 S) and hydrogen (H 2 ). The sulfidation was carried out at atmospheric pressure with a mixture having a composition of 40% by volume. The sulfidation reaction of the catalyst is obtained in two stages, the first stage being carried out in a stage heated to a controlled temperature (5 캜 / min), the second stage being 1.5 hours at the final temperature of the sulfiding reaction of 300 캜. Perform at the stage of. After the sulfidation reaction, the catalyst is cooled under nitrogen until it reaches room temperature. Part of the product is transferred under nitrogen atmosphere for sulfidation analysis. The remainder is separated from nitrogen and used for the characterization of the autoignition behavior and for the determination of hydrodesulfurization activity of gas oils.
S/Co + Mo의 몰비 측정치 및 황화 반응도는 하기 표에 기재하였다. 황화 반응도는 S/(Co + Mo) 몰비 측정치 및 S/(Co + Mo) 몰비 이론치간의 비에 100을 곱한 값으로 정의되며, 산화물리브덴 MoO3 및 산화코발트 CoO의 각각의 해당 황화물 MoS2 및 Co9S8로의 총 전환도에 해당하는 상기의 몰비 이론치는 [S/(Co + Mo)]이론 = 1.67이다.Molar ratio measurements and sulfidation reactivity of S / Co + Mo are listed in the table below. Sulfide reaction is S / (Co + Mo) molar ratio measurement and S / (Co + Mo) molar ratio is defined as the value obtained by multiplying 100 to a ratio between a theoretical value, an oxide molybdenum MoO 3, and each of the corresponding sulfide of cobalt oxide CoO MoS 2 and The above molar ratio theoretical value corresponding to the total conversion to Co 9 S 8 is [S / (Co + Mo)] theory = 1.67.
자동 발화 테스트는 UN 규격에 의하여 정의되는 테스트로서, 이는 위험 물질을 4.2류로 분류하였다. 특성화된 물질의 감도에 대한 추가의 정보를 얻기 위하여 변형된 테스트를 사용한다.The automatic ignition test is a test defined by the UN standard, which classifies dangerous substances into class 4.2. Modified tests are used to obtain additional information on the sensitivity of the characterized material.
UN 규격의 테스트 (코드 IMDG): 모서리가 10 ㎝인 격자형 시험관에 촉매를 넣고; 시험관의 중앙에는 촉매로 충전된 1 ℓ 시험관 온도의 승온을 기록할 수 있는 열전쌍을 도입하였다. 사전에 140℃로 예열된 대기중의 환기 오븐의 내부에 시험관 및 열전쌍 세트를 배치하였다. 24 시간동안, 건조 오븐 및 촉매 입방체의 온도를 기록하였다. 촉매는 자동 발화성을 나타냈으며, 이 온도에서는 테스트 24 시간 동안 200℃를 초과하였다. 그리하여, 이는 위험 물질 분류에서 4.2류, 고형물 3190의 군에 속하게 된다.Testing of the UN standard (code IMDG): the catalyst was placed in a lattice test tube with a corner of 10 cm; In the center of the test tube was introduced a thermocouple capable of recording an elevated temperature of a 1 L test tube temperature filled with a catalyst. A set of test tubes and thermocouples were placed inside an atmospheric ventilation oven previously preheated to 140 ° C. For 24 hours, the temperature of the drying oven and catalyst cubes was recorded. The catalyst exhibited autoignition, at which temperature exceeded 200 ° C. for 24 hours of testing. Therefore, it belongs to class 4.2, solid 3190 in the classification of dangerous substances.
자동 발화 온도를 측정하기 위한 변형된 테스트는 촉매 입방체의 내부 온도가 200℃를 초과하지 않을 때까지 건조 오븐의 온도를 약 140℃에서 10℃씩 변화시키는 것을 제외하고는 동일한 작업 모드로 실시한다. 각각의 온도에서, 새로운 1 ℓ의 촉매를 테스트한다. 자동 발화의 임계 온도(또는 TCAE)의 개념은 특징적인 촉매의 자동 발화 양상을 개시하기 이전의 건조 오븐의 최소 온도로서 정의된다.A modified test to determine the autoignition temperature is conducted in the same mode of operation except that the temperature of the drying oven is changed from about 140 ° C. to 10 ° C. until the internal temperature of the catalyst cube does not exceed 200 ° C. At each temperature, fresh 1 liter of catalyst is tested. The concept of the critical temperature (or TCAE) of autoignition is defined as the minimum temperature of the drying oven before initiating the autoignition behavior of the characteristic catalyst.
자동 발화 테스트와 동시에, 촉매를 질소 대기하에서 가스유의 수소화탈황 테스트 유닛의 반응기에 충전시켰다. 촉매의 설정 모드는 시간당 촉매 1 ℓ당 가스유 2 ℓ의 유속에서, 3 ㎫의 수소압에서, 400 ℓ/ℓ의 오일에 대한 수소 비율로 실험한 수소 유량의 존재하에서 상온에서 350℃로 점진적으로 승온시켜 얻는다. 24 시간의 안정화후, 액상 유출물을 15 시간 동안 수집하고, 잔류 황 비율은 X선 형광 분석에 의하여 측정하고, 이를 가스유의 초기값과 비교하였다. 활성도 모델은 반응도 1.5를 채택한 수학식을 사용하였다. 상대적 중량 활성도 (RWA)는 테스트한 촉매의 활성도와, 액상 공급물중의 DMDS (디메틸디설피드)를 첨가하여 현장내 모드로 동일한 황화 산화물 촉매의 활성도간의 비율에 의하여 측정한다.Simultaneously with the autoignition test, the catalyst was charged to the reactor of the hydrodesulfurization test unit of gas oil under a nitrogen atmosphere. The setting mode of the catalyst is gradually increased to 350 ° C. at room temperature in the presence of a hydrogen flow rate tested at a hydrogen rate of 400 L / L oil at a flow rate of 2 L gas oil per liter of catalyst per hour, at a hydrogen pressure of 3 MPa. Obtained by raising the temperature. After 24 hours of stabilization, the liquid effluent was collected for 15 hours and the residual sulfur ratio was measured by X-ray fluorescence analysis and compared with the initial value of gas oil. As the activity model, the equation adopting the reactivity 1.5 was used. Relative weight activity (RWA) is measured by the ratio between the activity of the catalyst tested and the activity of the same sulfide oxide catalyst in the in-situ mode with the addition of DMDS (dimethyldisulfide) in the liquid feed.
실시예 2: 상온에서의 산화 부동화Example 2: Oxidative Passivation at Room Temperature
실시예 1에서 사용한 것과 동일한 촉매를 황화 처리하고 (실시예 1과 동일한 조건을 사용함), 상온에서 질소하에 세정한 후, 상온 (20℃)에서의 산화 부동화로 지칭되는 절차에 의하여 부동화 처리하였다. 이러한 처리는 2 개의 단계로 수행된다. 제1의 단계는 7.6 ㎪의 산소 분압을 포함하는 무수 가스류 (공기+질소)하에서의 처리로 이루어진다. 촉매는 (상기 온도의 하강에 의하여 측정한) 황화물상에 대한 산소의 화학흡착과 관련한 발열 효과가 소실될 때까지 상기의 산소 분압을 유지한다. 제2의 단계는 무수 공기인 산소 분압 (21.3 ㎪)이 되도록 희석제 가스 (질소)의 공급을 중단하여 얻는다. 촉매를 산소 및 황화물상의 상호작용과 관련된 발열 효과가 소실될 때까지 기류하에 배치한다. 이러한 부동화 처리후, 촉매를 질소 대기하에 저장한다. 시료의 일부분을 질소하에서 취하여 부동화 처리중에 고정된 산소의 함량 및 황화 반응도를 분석하였다. 나머지는 동일한 대기하에서 분리하여 자동 발화 양상의 특성화 및, 가스유의 수소화탈황 활성의 측정에 사용하였다.The same catalyst as used in Example 1 was sulfided (using the same conditions as in Example 1), washed under nitrogen at room temperature and then immobilized by a procedure referred to as oxidative passivation at room temperature (20 ° C.). This process is performed in two steps. The first step consists of treatment under an anhydrous gas stream (air + nitrogen) comprising an oxygen partial pressure of 7.6 kPa. The catalyst maintains the above oxygen partial pressure until the exothermic effect associated with chemisorption of oxygen on the sulfide phase (as measured by the drop in temperature) is lost. The second step is obtained by stopping the supply of diluent gas (nitrogen) so as to have an oxygen partial pressure (21.3 kPa) which is anhydrous air. The catalyst is placed under airflow until the exothermic effects associated with the interaction of the oxygen and sulfide phases are lost. After this passivation treatment, the catalyst is stored under a nitrogen atmosphere. A portion of the sample was taken under nitrogen to analyze the content of oxygen and sulfidation reactivity fixed during the passivation treatment. The remainder was separated under the same atmosphere and used to characterize the autoignition behavior and to measure the hydrodesulfurization activity of the gas oil.
S/Co + Mo 몰비, 황화 반응도 및 부동화 처리중 화학흡착된 산소 함량을 하기 표에 기재하였다. 화학흡착된 산소 함량은 부동화된 촉매상에서 측정한 점화시 손실율 측정치 [4 시간 동안 500℃에서 대기하에서 모플(moufle) 로를 사용한 처리]와, 이상적인 황화 반응도에 대하여 정의된 점화시 손실율 이론치간의 차이에 의하여 결정된다.The S / Co + Mo molar ratio, sulfidation reactivity and chemisorbed oxygen content during passivation treatment are listed in the table below. The chemisorbed oxygen content is based on the difference between the ignition loss rate measurements measured on the immobilized catalyst (treatment using a moufle furnace in air at 500 ° C. for 4 hours) and the ignition loss rate theory defined for the ideal sulfidation reactivity. Is determined by.
"촉매 SP2"로 지칭된 촉매에 대한 활성 테스트는 실시예 1에서 기재한 것과 동일한 테스트 프로토콜을 사용하였다.The activity test for the catalyst referred to as "catalyst SP2" used the same test protocol as described in Example 1.
실시예 3: 무수 산화 류하에서의 중간 온도에서의 열 처리에 의해 황화 처리한 촉매의 부동화Example 3: Passivation of Sulfurized Catalyst by Heat Treatment at Medium Temperature Under Anhydrous Oxidation
실시예 1에서 사용한 것과 동일한 촉매를 황화 처리하고 (실시예 1과 동일한 조건하에서), 상온에서 질소하에 세정하였다. 그후, 부동화 온도를 50℃로 한 것을 제외하고, 실시예 2에서 사용한 것과 동일한 부동화 프로토콜을 사용하여 촉매를 부동화 처리하였다. 일단 촉매가 상기의 온도에 있게 되면, 7.6 ㎪의 산소 분압을 사용한 무수 공기/질소류를 반응 구역에 투입하였다. 황화물상에 대한 산소의 화학흡착과 관련된 발열 효과가 소실된 후, 질소류를 중단하고, 촉매를 기류(21.3 ㎪의 산소 분압)하에서만 유지하였다. 온도가 50℃가 될 때까지 이러한 대기를 유지한 후, 이를 상온으로 질소하에 냉각시켰다. 그리하여 얻은 촉매 SP3를 실시예 2에 기재된 것과 유사한 방법에 의하여 특성화하였다.The same catalyst as used in Example 1 was sulfided (under the same conditions as Example 1) and washed under nitrogen at room temperature. The catalyst was then passivated using the same passivation protocol as used in Example 2 except that the passivation temperature was set at 50 ° C. Once the catalyst was at this temperature, anhydrous air / nitrogen stream with an oxygen partial pressure of 7.6 kPa was introduced into the reaction zone. After the exothermic effect associated with chemisorption of oxygen to the sulfide phase was lost, the nitrogen flow was stopped and the catalyst was maintained only under air flow (oxygen partial pressure of 21.3 kPa). This atmosphere was maintained until the temperature reached 50 ° C. and then cooled to room temperature under nitrogen. The catalyst SP3 thus obtained was characterized by a method similar to that described in Example 2.
실시예 4: 낮은 산소 분압하에서 산화 류하에서의 처리에 의해 황화 처리한 촉매의 부동화Example 4 Passivation of Sulfurized Catalysts by Treatment under Oxidation Flow at Low Oxygen Partial Pressure
실시예 1에서 사용한 것과 동일한 촉매를 (실시예 1에 기재된 것과 동일한 조건하에서) 황화 처리하고, 이를 상온에서 질소하에 세정한 후, 이를 100℃의 온도까지 재가열하였다. 2.0 ㎪의 산소 분압을 포함하는 무수 공기/질소 혼합물로 이루어진 가스류를 도입하였다. 발열 효과가 모두 소실될 때까지 그리고 온도가 100℃가 될 때까지 상기 대기하에서 촉매를 유지하였다. 그리하여 상온까지 질소류하에서 냉각시켰다. 그리하여 얻은 촉매 SP4는 실시예 2와 유사한 방법에 의하여 특성화하였다.The same catalyst as used in Example 1 was sulfided (under the same conditions as described in Example 1), which was washed under nitrogen at room temperature and then reheated to a temperature of 100 ° C. A gas stream consisting of anhydrous air / nitrogen mixture with an oxygen partial pressure of 2.0 kPa was introduced. The catalyst was held under the atmosphere until the exothermic effect disappeared and the temperature reached 100 ° C. Thus, the mixture was cooled to room temperature under nitrogen flow. The catalyst SP4 thus obtained was characterized by a similar method as in Example 2.
실시예 5: 무수 산화 류하에서 고온에서의 열 처리에 의해 황화 처리한 촉매의 부동화Example 5 Passivation of a Sulfurized Catalyst by Heat Treatment at High Temperature Under Anhydrous Oxidation
실시예 1에서 사용한 것과 동일한 촉매를 (실시예 1과 동일한 조건하에서) 상온에서 질소하에 세정한 후, 이를 120℃로 가열하였다. 7.6 ㎪의 산소 분압을 포함하는 무수 공기/질소 혼합물로 이루어진 가스류를 도입하였다. 발열 효과가 소실된 후, 질소류를 중단하고, 촉매를 기류(21.3 ㎪의 산소 분압)하에서만 유지하였다. 온도가 120℃가 될 때까지 이러한 대기를 유지하였다. 이를 상온으로 질소하에 냉각시켰다. 그리하여 얻은 촉매 SP5를 실시예 2에 기재된 것과 유사한 방법에 의하여 특성화하였다.The same catalyst as used in Example 1 was washed under nitrogen at room temperature (under the same conditions as Example 1) and then heated to 120 ° C. A gas stream consisting of anhydrous air / nitrogen mixture with an oxygen partial pressure of 7.6 kPa was introduced. After the exothermic effect disappeared, the nitrogen flow was stopped and the catalyst was maintained only under the air stream (oxygen partial pressure of 21.3 kPa). This atmosphere was maintained until the temperature reached 120 ° C. It was cooled to room temperature under nitrogen. The catalyst SP5 thus obtained was characterized by a method similar to that described in Example 2.
황화 반응도값은 황화물상의 이산화황으로의 산화 반응 개시로 인하여 상기의 촉매보다 낮았다.The sulfidation reactivity value was lower than that of the catalyst due to the initiation of the oxidation reaction to sulfide on sulfur dioxide.
실시예 6: 고정상에서의 무수 산화 류하에서의 열처리에 의해 황화 처리한 촉매의 부동화Example 6 Passivation of Sulfurized Catalyst by Heat Treatment Under Anhydrous Oxidation in a Fixed Bed
실시예 1에서 사용한 것과 동일한 촉매를 (실시예 1에 기재된 것과 동일한 조건하에서) 황화 처리하고, 이를 상온에서 질소하에 세정하였다. 그후, 부동화 온도를 100℃로 한 것을 제외하고, 실시예 2에서 사용한 것과 동일한 부동화 프로토콜을 사용하여 촉매를 부동화 처리하였다. 일단 촉매가 부동화 온도에 있게 되면, 7.6 ㎪의 산소 분압을 포함하는 무수 공기/질소류를 투입하였다. 황화물상에 대한 산소의 화학흡착과 관련된 발열 효과가 소실된 후, 질소류를 중단하고, 촉매를 기류(21.3 ㎪의 산소 분압)하에서만 유지하였다. 발열 효과가 소실된 후, 촉매를 상온으로 질소하에 냉각시켰다. 그리하여 얻은 촉매 SP6를 실시예 2에 기재된 것과 유사한 방법에 의하여 특성화하였다.The same catalyst as used in Example 1 was sulfided (under the same conditions as described in Example 1) and it was washed under nitrogen at room temperature. The catalyst was then passivated using the same passivation protocol as used in Example 2 except that the passivation temperature was set at 100 ° C. Once the catalyst was at the passivation temperature, anhydrous air / nitrogen stream containing an oxygen partial pressure of 7.6 kPa was introduced. After the exothermic effect associated with chemisorption of oxygen to the sulfide phase was lost, the nitrogen flow was stopped and the catalyst was maintained only under air flow (oxygen partial pressure of 21.3 kPa). After the exothermic effect disappeared, the catalyst was cooled under nitrogen to room temperature. The catalyst SP6 thus obtained was characterized by a method similar to that described in Example 2.
실시예 7: 고정상에서의 습윤 산화 류하에서의 열처리에 의해 황화 처리한 촉매의 부동화Example 7 Passivation of Sulfurized Catalysts by Heat Treatment Under Wet Oxidation in a Fixed Bed
제조 프로토콜은 무수 대기를 습윤 대기로 교체한 것을 제외하고는 실시예 6과 유사하다. 가스 혼합물은 7.6 ㎪의 산소 분압 및 3.0 ㎪의 수증기 분압을 포함한다. 그리하여 얻은 촉매 SP7을 실시예 2에 기재된 것과 유사한 방법에 의하여 특성화하였다. 물의 함량은 120℃에서 질소하에 열중량 측정법에 의하여 측정하였다.The production protocol is similar to Example 6 except that the dry atmosphere was replaced with a wet atmosphere. The gas mixture includes an oxygen partial pressure of 7.6 kPa and a steam partial pressure of 3.0 kPa. The catalyst SP7 thus obtained was characterized by a method similar to that described in Example 2. The content of water was measured by thermogravimetric method at 120 ° C. under nitrogen.
실시예 8: 무수 산화 류하에서의 열처리에 의해 이동상 황화 처리한 촉매의 부동화Example 8 Passivation of Catalysts Treated with Mobile Phase Sulfuration by Heat Treatment Under Anhydrous Oxidation
실시예 1에서 사용한 것과 동일한 촉매를 300℃의 온도에서 3 시간 동안 60/40의 부피 조성을 갖는 H2S/H2 혼합물에 의한 대기압하에서 회전 시험관의 파일럿 유닛에서 황화 처리하였다. 촉매는 시험관으로부터 꺼내어 질소 세정하에서 유지되는 엔클로저내에 보관하였다. 회전 유닛을 질소하에서 세정하고, 이를 100℃의 온도로 냉각시켰다. 다시 촉매를 질소 대기하의 회전 유닛의 충전 깔때기에 다시 넣었다. 촉매의 중량 유닛에 의하여 도입된 산소량이 실시예 6에서 결정한 양의 1.5 배 이상이 되지 않도록, 즉 황화 처리한 촉매 1 ㎏/h에 대하여 공기 200 Nlt/h가 되도록 결정한 유속으로 오븐에 순수한 공기를 도입하였다. 오븐내의 생성물의 체류 시간은 100℃에서 3 시간이었다. 그후, 질소로부터 시료를 취하여 실시예 1에 기재된 것과 동일한 방법에 의하여 분석을 실시하였다.The same catalyst as used in Example 1 was sulfided in a pilot unit of a rotating test tube under atmospheric pressure with a H 2 S / H 2 mixture having a volume composition of 60/40 at a temperature of 300 ° C. for 3 hours. The catalyst was removed from the test tube and stored in an enclosure maintained under a nitrogen wash. The rotary unit was washed under nitrogen and cooled to a temperature of 100 ° C. The catalyst was again put back into the charging funnel of the rotary unit under nitrogen atmosphere. Pure air is introduced into the oven at a flow rate determined such that the amount of oxygen introduced by the weight unit of the catalyst is not more than 1.5 times the amount determined in Example 6, that is, the air is 200 Nlt / h with respect to 1 kg / h of the sulfided catalyst. Introduced. The residence time of the product in the oven was 3 hours at 100 ° C. Then, the sample was taken from nitrogen and analyzed by the same method as described in Example 1.
실시예 9: 특성화 결과 및 결론Example 9: Characterization Results and Conclusions
가스유의 수소화탈황 반응 활성, 상대적 중량 활성 (RWA) 및 자동 발화의 임계 온도(TCAE):Hydrodesulfurization activity, relative weight activity (RWA) and critical temperature (TCAE) of autoignition of gas oils:
결론적으로, 부동화 처리되지 않은 황화 촉매는 대기하에서 처리될 수 없는 것이 명백하다. 상온에서의 산화 부동화 단독은 대기하에서 생성물의 특정의 취급을 허용하기 위하여 자동 발화 양상을 개선시킨다. 그럼에도 불구하고, 생성물은 민감하며, 커다란 수소화처리 유닛에서 대기하에 충전을 허용하는 것은 권장하지 않는다. 7 ㎪ 이상이 바람직한 산소 분압하에서 산화 부동화를 위한 열 처리 (50℃ 이상의 온도)는 자동 발화 특성을 충분히 감소시키기 위하여 유용하다. 허용 가능한 것으로 간주하는 값은 100℃의 TCAE로부터 정하는 것이 바람직할 것이다. 자동 발화 성질을 개선시킬 수 있는 작동 기준은 온도, 산소 분압, 수증기 분압, 공정 유형 등이 있다. 온도는 황화물상을 크게 개선시키기 위하여 50℃ 이상으로 충분히 높아야 한다. 산소 함량은 수행하는 실시예에 따라 바람직하게는 2.0 ㎪ 이상으로 충분하여야 하나, 이러한 값에 한정되는 것은 아니다.In conclusion, it is evident that the unpassivated sulfiding catalyst cannot be treated under air. Oxidative immobilization alone at room temperature improves the autoignition behavior to allow for specific handling of the product under air. Nevertheless, the product is sensitive and it is not recommended to allow charging under air in large hydrotreating units. Heat treatment (temperature above 50 ° C.) for oxidative passivation under an oxygen partial pressure of preferably 7 Pa or more is useful to sufficiently reduce the autoignition characteristics. Values deemed acceptable will preferably be determined from TCAE at 100 ° C. Operating criteria that can improve the autoignition properties include temperature, oxygen partial pressure, steam partial pressure, and process type. The temperature should be high enough above 50 ° C. to greatly improve the sulfide phase. Oxygen content is preferably 2.0 kPa or more, depending on the embodiment to be carried out, but is not limited to these values.
다른 한편으로, 산화 반응의 강도를 조절하기 위하여 온도/산소 분압의 쌍을 조절하여야만 한다. 실시예 5는 부동화가 매우 효과적이지만, 황화 반응도 (이산화황의 증발에 의한 황의 손실) 및 촉매 활성을 희생하면서 수행된다. 120℃ 이하의 온도가 이롭다. 2 단계의 부동화가 종종 바람직한 것으로 밝혀졌다. 마지막으로, 가스중의 수분의 추가는 고정상 보다는 이동상 로에서의 통과뿐 아니라, 부동화 효과를 개선시킬 수 있도록 한다.On the other hand, the temperature / oxygen partial pressure pair must be adjusted to control the intensity of the oxidation reaction. Example 5 is passivated very effectively, but is performed at the expense of sulfidation reactivity (loss of sulfur by evaporation of sulfur dioxide) and catalytic activity. Temperatures below 120 ° C. are advantageous. Two levels of passivation have often been found to be desirable. Finally, the addition of moisture in the gas makes it possible to improve passivation effects as well as passage through the mobile phase rather than the stationary phase.
또다른 한편으로는, 수증기의 존재 또는 부재하에서의 열처리에서의 산화 부동화의 신규한 방법은 수소화처리 반응을 위한 황화물 상의 촉매 성능을 변경시키지 않는다는 점에 유의한다.On the other hand, it is noted that the novel method of oxidative passivation in heat treatment in the presence or absence of water vapor does not alter the catalytic performance of the sulfide phase for the hydrotreating reaction.
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| CA (1) | CA2499696C (en) |
| DE (1) | DE60327638D1 (en) |
| FR (1) | FR2845014B1 (en) |
| WO (1) | WO2004028691A2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2854335B1 (en) * | 2003-04-30 | 2009-03-20 | Eurecat Sa | OFF-SITE TREATMENT OF HYDROGENATION CATALYSTS |
| FR2874838B1 (en) * | 2004-09-08 | 2006-11-24 | Inst Francais Du Petrole | PROCESS FOR SULFURIZING HYDROTREATING CATALYSTS |
| CN102284299B (en) * | 2010-06-18 | 2013-03-27 | 中国石油化工股份有限公司 | Vulcanization method for hydrogenation catalyst and application thereof |
| CN105233881B (en) * | 2014-07-11 | 2018-03-20 | 中国石油化工股份有限公司 | Sulfur-resistant transformation catalyst deep cooling is passivated pretreating process |
| WO2019117677A2 (en) * | 2017-12-14 | 2019-06-20 | 주식회사 포스코 | Method for producing metal sulfide catalyst, method for maintaining performance of same, and method for regenerating same |
| CN113083376A (en) * | 2019-12-23 | 2021-07-09 | 内蒙古伊泰煤基新材料研究院有限公司 | Passivation method of hydrocracking catalyst |
| CN113117763B (en) * | 2019-12-31 | 2023-01-10 | 中国石油化工股份有限公司 | Passivation method of vulcanization type hydrogenation catalyst |
| CN115254124B (en) * | 2021-04-30 | 2024-03-12 | 中国石油化工股份有限公司 | Preparation method of pre-reduction hydrogenation catalyst |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3122497A (en) * | 1960-09-01 | 1964-02-25 | Sinclair Research Inc | Method of reactivating a cracking catalyst |
| US3146188A (en) * | 1961-02-09 | 1964-08-25 | Sinclair Research Inc | Process for cracking a residual oil containing metallic impurities |
| US3287257A (en) * | 1964-08-18 | 1966-11-22 | Union Oil Co | Activation of hydrocarbon conversion catalysts employed in the hydrocracking of hydrocarbons |
| NL184371C (en) * | 1974-04-25 | 1989-07-03 | Shell Int Research | METHOD FOR DECOMMISSIONING A HYDROGENATION REACTOR, AND A METHOD FOR THE CATALYTIC HYDROGENATION OF A SULFUR COMPOUNDS. |
| FR2725381B1 (en) * | 1994-10-07 | 1996-12-13 | Eurecat Europ Retrait Catalys | OFF-SITE PRETREATMENT PROCESS FOR A HYDROCARBON TREATMENT CATALYST |
| US5922638A (en) * | 1996-06-12 | 1999-07-13 | Europeene De Retraitement De Catalyseurs Eurecat | Process for presulfurizing hydrotreatment catalysts |
| FR2749779B1 (en) * | 1996-06-12 | 1998-09-11 | Eurecat Europ Retrait Catalys | PROCESS FOR PRESULFURIZING HYDROTREATMENT CATALYSTS |
| DK1272272T3 (en) * | 2000-04-11 | 2012-03-05 | Eurecat Europ Retrait Catalys | Process for sulfiding an additive-containing catalyst |
| US6509291B2 (en) * | 2000-04-11 | 2003-01-21 | Akzo Nobel N.V. | Process for sulfiding a catalyst containing an S-containing additive |
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2002
- 2002-09-27 FR FR0212034A patent/FR2845014B1/en not_active Expired - Lifetime
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- 2003-09-25 KR KR1020057005140A patent/KR101017663B1/en active IP Right Grant
- 2003-09-25 US US10/529,378 patent/US7501376B2/en active Active
- 2003-09-25 JP JP2004539139A patent/JP4991106B2/en not_active Expired - Lifetime
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- 2003-09-25 EP EP03773812A patent/EP1545774B1/en not_active Expired - Lifetime
- 2003-09-25 DE DE60327638T patent/DE60327638D1/en not_active Expired - Lifetime
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| EP1545774A2 (en) | 2005-06-29 |
| JP2006500209A (en) | 2006-01-05 |
| KR101017663B1 (en) | 2011-02-25 |
| US20060154813A1 (en) | 2006-07-13 |
| DE60327638D1 (en) | 2009-06-25 |
| CA2499696A1 (en) | 2004-04-08 |
| FR2845014A1 (en) | 2004-04-02 |
| EP1545774B1 (en) | 2009-05-13 |
| WO2004028691A3 (en) | 2004-05-13 |
| CA2499696C (en) | 2011-01-18 |
| WO2004028691A2 (en) | 2004-04-08 |
| JP4991106B2 (en) | 2012-08-01 |
| US7501376B2 (en) | 2009-03-10 |
| FR2845014B1 (en) | 2006-01-13 |
| AU2003282191A1 (en) | 2004-04-19 |
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